CA1307864C - Low smoke modified polypropylene insulation compositions and process for the preparation thereof - Google Patents
Low smoke modified polypropylene insulation compositions and process for the preparation thereofInfo
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- CA1307864C CA1307864C CA000522194A CA522194A CA1307864C CA 1307864 C CA1307864 C CA 1307864C CA 000522194 A CA000522194 A CA 000522194A CA 522194 A CA522194 A CA 522194A CA 1307864 C CA1307864 C CA 1307864C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Organic Insulating Materials (AREA)
Abstract
A B S T R A C T
LOW SMOKE MODIFIED POLYPROPYLENE INSULATION COMPOSITIONS
AND PROCESS FOR THE PREPARATION THEREOF
A flame retardant insulation composition comprising the following components:-(a) in the range of from 5 to 40 per cent by weight of a hydrogenated monoalkylarene (A)-conjugated diene (B) block copolymer contain at at least two A blocks and at least one B
block;
(b) in the range of from 1 to 20 per cent by weight of a plasticizer;
(c) in the range of from 1 to 40 per cent by weight of functionalized or not functionalized polypropylene;
(d) in the range of from 10 to 85 per cent by weight of a hydrated inorganic filler which optionally has been surface treated with a coupling agent;
(e) and optionally in the range of from 0.25 to 10 per cent by weight of a functionalized low molecular weight polypropylene wax, which composition in the absence of component (e) contains a hydrated inorganic filler which has been surface treated with a coupling agent, and process for the preparation thereof by combining components (a) to (d) and optionally (a) to (e).
LOW SMOKE MODIFIED POLYPROPYLENE INSULATION COMPOSITIONS
AND PROCESS FOR THE PREPARATION THEREOF
A flame retardant insulation composition comprising the following components:-(a) in the range of from 5 to 40 per cent by weight of a hydrogenated monoalkylarene (A)-conjugated diene (B) block copolymer contain at at least two A blocks and at least one B
block;
(b) in the range of from 1 to 20 per cent by weight of a plasticizer;
(c) in the range of from 1 to 40 per cent by weight of functionalized or not functionalized polypropylene;
(d) in the range of from 10 to 85 per cent by weight of a hydrated inorganic filler which optionally has been surface treated with a coupling agent;
(e) and optionally in the range of from 0.25 to 10 per cent by weight of a functionalized low molecular weight polypropylene wax, which composition in the absence of component (e) contains a hydrated inorganic filler which has been surface treated with a coupling agent, and process for the preparation thereof by combining components (a) to (d) and optionally (a) to (e).
Description
loW SMOKE MCDIFIED POLYPROPYLENE INSUL~TION CCMPOSITIONS
AND PROCESS FOR THE PREPAR~TION THEREOF
The invention relates to a flame retardant insulation oomposi-tion and to a pxocess for the p~eparation thereof.
Th~ m~st ocmm~n ~ethod for reducmg the flammability of wire and cable insulation and jacketing materials is the use of an ~;~ S or~anic bromine or chlorine c~mpound alo~g with antimony oxide.
This system is very effective as a flame retard3nt, but such materials produce a dense black smoke when burned, and also produce hydrogen chloride or hydrogen brcmide, which are both corrosi~e and toxic. Because of this, there has been a great deal of lnterest in flame retarded s~stems that produce lower amounts of smoke and to~ic and corrosive gases when they are burned. There appear to be ;~ ~ tw~ main approaches that are beLng followed to met this goal. The first is to elimunate halogens from the system and use instead large loadings of alumina trihydrate, another comm~n fire retardant, or the simQlar filler ~agnesium hydroxide. The second is to de~elop additives that reduce the smoke and acid gas production of the halogenated systems. In addition to low smoke and low toxicity these compositions must also have attractive physical prcperties in order to be used for wire and cable applications. ~hese properties ~ Lnclude hardn~ess, abrasion resistance, environmental stability, deformation rPsistance~ low temperature flexibility, oil resistance and~good e1ectrical properties. At present there are no low-smDke, low-lboxicity, ~lame-retardant materials which are readily available although sQme new materials including metal hydrate filled poly-eth~lene are becoming available.
Mbtal~hydra~ s such as alumina trihydrate and magnesiumtydrc~ide c~ntain water bonded to a crystal s~ructure with the metal atom. When heated to a sufficiently high temperature these cospc~ods decompose and relea~e water which subsequently vaporizes ::, : . :
: .
~ ~ , - ::3L3Vt~ 9, This process of decomposition and vaporization absorbs heat, thus slcwing dcwn the initial heating of the insulation material and consequently slows down the subsequent burning of the material.
After this cooling effect is overwhelmed however, the presence of the metal hydrates has little effect on the subsequent process of burning. Unlike the halogenated flame retardant co~position, metal hydrate compositions with non-halogenated polyolefins break down quickly into monomer units and burn relatively cleanly without a great deal of smoke production. In addition, since metal hydrates only add water to the syst3m, they should not increase the emission of taxic or corrosi~e gases beyona wha~ alread~ would be produced ~y the system.
Magnesium hydroxide fillers along with alumina trihydrate fillers have been used in flame retardant polypropylene co~positions.
Alumina trihydrate is generally more effective as a flame retardant than is magnesium hydroxide due to the greater amount of water incorporated in that filler; however, magnesium hydroxide has specific advantages, for example, better processability when incorporated into a polyolefin co~position and a higher deccmposition temperature than alumina trihydrate (330 C versus 230 C3. This ; increase in deoomposition temperature allows a flame retardant polymer oomposition containing magnesium hydroxide to be processed at a higher temperature than a ccmpound with alumuna trihydrate.
e hi~her processing ten~eratures allow much faster processing due to lower viscosities.
~ Polypropylene, which is readily available at a reasonable ; cost, has found nany industrial uses because of its desirable physical properties, such as easa of fabrication by all conventional methods; high melting pomt of stereoregular, e.g., isotactic, pvlypropylene and compatibility with m~ny other commercial resins, which pernits a large number of blends having specific properties.
Brittleness in these compositions can be reduc~d either by copoly-merizing propylene with ethylene to form block copolymers or by blending hom~polypropylene with rubbers.
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A flame retardant insulation composition has now been found that for~s a self-extinguishing, low smoke and halogen free insulation composition which exhibits high ultimate elongation and is relatively easy to process.
It has been found that functionalizing the polypropylene in an insulation ~lend improves the physical properties, e.g., tensile strength and elongationO It has been found that the brittleness problem can be essen~ially eliminated by using functionalized polypropylene. The functionalized polypropylene has reactive groups grafted to it which will attach to a filler producing bonding between the polypropylene and the filler, thereby producing better physical properties.
; It has also been found that conventional magnesium ~ hydroxide fillers cannot be successfully blended into rubber `; modified polypropylene compositions in the absence of component (e), being a functionalized low molecular weight polypropylene ; wax. These compositions when filled to a reasonable loading of `;; magnesium hydroxide cannot be processed due to agglomeration of the filler particles. When agglomeration occurs the effective ~20 particle size of the filler is increased dramatically and therefore the processability and the properties of the end product are degraded.
Accordingly, it would be desirable to provide a :
; ; magnesium hydroxide filler which has good physical properties and ~ would not adversely affect the processability by agglomeration.
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Fillers may therefore be surface treated with a coupling agent prior to blending to enhance the bonding between the functionalized polypropylene and the filler.
Furthermore, it has been found that addition of a small amount of a functionalized low molecular weight polypropylene wax to the composition dramatically increases the tensile strength of these compositions.
Accordingly, the present invention provides a flame retardant insulation composition comprising the following components:-(a) in the range of from 5 to 40 percent by weight of a hydrogenated monoalkylarene (A)-conjugated diene (B) block copolymer containing at least two A blocks and at least one B
block;
(b) in the range of from 1 to 20 percent by weight of a saturated hydrocarbon, mineral oil, or a hydrogenated or saturated hydro-carbon resin;
(c) in the range of from 1 to 40 percent by weight of polypropy-lene optionally having an unsaturated polycarboxylic group grafted thereto;
(d) in the range of from 10 to 85 percent by weight of a metal salt hydrate which optionally has been surface treated with a : coupling agent;
(e) and optionally in the range of -from 0.25 to 10 percent by weight of a functionalized low molecular weight polypropylene ~ wax, which composition in the absence of component (e) contains a '~
; ''`"' -, :~
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- 4a - 63293-272 metal salt hydrate which has been surface treated with a coupling agent.
The compositions of the present invantion are prepared by combining the required components in the correct proportions in conventional blending equip~ent such as a rubber mill or mixer, for example, a Banbury mixer. This is usually done above the melting temperature of the polymeric materials.
The not functionalized polypropylene or homopoly-propylene preferably should be isotactic and may be, for example, of the type corresponding to Shell PP-5944 S*, PP-5520*, and PP
DX-5088*, available from Shell Chemical Company, Houston, Texas.
Most commercial isotactic polypropylenes are suitable in the composition~ of this invention. Syndiotactic homopolymers also can be used.
Functionalized polypropylenes are well known in the art and may be prepared, for examplej according to the procedure described in US patent specification 3,480,580 or 3,481,910.
These polymers may be prepared from homopolypropylene which preferably should be isotactic and may be, for example, the types corresponding to Shell PP-5944 S, PP-5520 and PP DX-5088 mentioned hereinbefore. Syndiotactic homopolymers also can be used. A
preferred functionalized polypropylene is maleic anhydride functionalized polypropylene of the type corresponding to Plexar 2110*, available fro~ Northern Petrochemical Company, Rolling ~ Meadows, Illinois, U.S.A.
; * Trade Mark :
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- 4b - 63293-2722 The fillers used in the present invention are the hydrated inorganic fillers, e.g. hydrated aluminium oxides (A1203.3H20 or Al(OH)3), hydrated magnesia, hydrated calcium silicate zinc borate. Of these compounds, the most preferred are hydrated :
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alumunium oxide and magnesium hydroxide.
Coupling agent~ may include fatty acid metal salts, for example oleates ox stearates; silanes, maleates, titanates and zirco-aluminates.
The filler particle size is relatively non-important and may be in accordance with those sizes used by the prior art. Preferred particle sizes axe less than 5 ~m. It has also been found that magnesium hydroxide fillers with a high aspect ratio crystallate shape and larger size are also less likely to agglomerate than those with a lower aspect ratio. Aspect ratios ~or the crystallites should be greater than 4 and mean secondary particle (agglcmerateJ
size should be less than 3 ~m and are preferably in the range of from 0.6 to 1.2 ~m.
Functionalized low molecular weight polypropylene waxes are well kncwn in the art and may be prepared, for example, from polymers prepared according to the procedures described in UOS.
pat~nt specifications 2,969,345 and 3,919,176. me ccnpositions according to the invention and containing such waxes preferably cGntain not functionalized polypropylene and may contain not functionalized polypropylene as well as functionalized polypxolylene.
A particularly preferred functionalized low molecular weight polypropylene wax is a normally solid thermoplastic ethylene-based polymer modified by monomers having reactive carboxylic acid groups, particularly a copol~mer of a ma~or proportion of ethylene and a m mor proportion, typically from 1 to 30, preferably from 2 to 20~ per cent by weight, of an ethylenically unsaturated carboxylic acid. Specific examples of such suit~ble ethylenically unsaturated carboKylic acids (which term includes mono- and polybasic acids, ~; ~ 30 acid anhydrides, and partial esters of polybasic aci~s) are acrylic a¢id, methacrylic acid, crDtonic acid, fumaric acid, maleic acid, itaoonic acid, maleic anhydride monomethyl maleate, monoethyl maleate, manomethyl fumarate, n~noethyl fumarat~e, tripropylene glycol monome~hyl ether acid maleate, or ethylene glycol moncphenyl ether acid maleate. The carbcxylic acid ~Dnomer is preferably selected from ~,B-ethylem cally unsaturated mono- and polycarboxylic acids and acid anhydrides having from 3 to 8 carbon atoms per .
~3~7~
molecule and partial esters of such polycarboxylic acids wherein the acid moiety has at least one carboxylic acid ~roup and the alcohol moiety has from 1 to 20 carbon atoms. me copolymer can also contain other copolymerizable monomers including an ester of acrylic acid. The comonomers can be co~bined in the copolymer in any way, for example, as random copolymers, as block or sequential copolymers, or as ~raft copolymers. Materials of these kinds and methods of making them are readily known in the art. Specific exa~ples of such copolymers are ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer, ethylene maleic acid copolymer and the like~
Functionalized low molecular weight polyprcpylene wax is available from, for example, Eastman Chemical Products Inc. under the trade name "Epolene E43"~
The hydrogenated monoalkyl arene-conjugated diene block copolymers useful in the present invention are well known in the art. m is block copolymer, for example, as defined in U.S. patent specification 4,110,303, has at least two monoalkenyl arene polymer end blocks A and at least one polymer mid block B of a substantially campletely hydrogenated conjugated diene polymer block, an ethylene-propylene polymer block or an ethylene-butene polymer block. me block copolymers employed in the present invention may have a variet~ of geometrical structures, since the invention doe s not depend on any specific geometrical struct.ure, but rather upon the chemical constitution of each of the polymer blocks. mus, the structures may be lmear, radial or branched so long as each copolymer has at least two polymer end blocks A and at least one polymEr mdd block B as defined hereinbefore. Methods for the preparation of such polymers are known in the art. Particular ~ 30 reference will be made to the use of lithium based catalysts and; ~ especially lithium alkyls for the preparation of the precursor polymers ~polymers before hydrogenation). U.S. patent specification 3,595,942 not only describes some of the polymers of the present invention but also describes suitable methods for their hydro-genation. rrhe structure of the polymers is determined by their method of polymerization. For example, linear polymers result by : .
:
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sequ~ntial introduction of the desired monomers into the reaction vessel when using such initiators as lithium-aLkyls or dilithio-stilbene and the like, or by coupling a two segment block copolymer with a difuntional coupling agent. Branched structures, on the other hand, may be obtained by the use of suitable coupling agents having a func*ionalit~v with respect to the precursor polymers of three or more. Cbupling may be effected with multifunctional coupling agents such as dihaloalkanes or alkenes and divinylbenzene as well as certain polar compDunds such as silicon halides, siloxanes or esters of monohydric alcohols with carbcxylic acids. The presence of any coupling residues in the polymer may be ignored for an ad~quate description of the polymers forming a part of the ccmpo-sitions of this invention. Likewise, in the generic sense, the specific structures also may be ignored. The invention applies especially to the use of selectively hydrogenated polymers having the configuration before hydrogenation of the following typical species:
polystyrene-polybutadiene-polystyrene (SBS) polystyrene-polyisoprene-polystyrene (SIS) poly(alpha-methylstyrene)-polybutadiene~poly(alpha-methylstyrene) and poly(alpha-methylstyrene)-polyisoprene-poly(alpha-methylstyrene).
It will be understood that both blocks A and B may be either homcpolymer or random cqpoly~er blocks as long as each block predomunat~s in at least one class of the monomers characterizing ~he blocks and as long as the A blocks individually predcminate in m~noalkenyl anenes and the B blocks individually predom~nate in dienes. me term "~noaIkenyl arene" ~ill be taken to include ; ~ especially styrene and its analogs and hom~lc~s including alpha-methylstyrene and ring-substituted styrenes, particularly ring-methylated styrenes. The preferred m~noalkenyl arenes are styrene and alpha-methylstyrene, and styrene is particularly preferred. me blocks B may oompris~ homopolymers of butadiene or isoprene and capolymers of one of these tw~ dienes with a monoalkenyl arene as ~; 35 long as the blocks B predcminate in conjugated diene units. When the monomer enployed is butadiene, it is preferred that between ~:
~.
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about 35 and about 55 mol per cent of the condensed butadiene units in the butadiene polymer block have l,2 configuration. Thus, when such a block is hydrogenated, the resulting product is, or resembles a regular copolymer block of ethylene and l-butene (EB). If the conjugated diene employed is isoprene, the resulting hydrogenated product is or resembles a regular copolymer block of ethylene and propylene (EP). Ethylene-butene or ethylene-propylene blocks prepared via direct polymerization and not by hydrogenation of conjugated diene polymer blocks are also contemplated by the present invention.
Hydrogenation of the precursor block copolymers, if required, is preferably effected by use of a catalyst comprising the reaction pro~ucts of an aluminium alkyl compound with nickel or cobalt carboxylates or alko~ides under such conditions as-to substantially completely hydrogenate at least 80% of the ali~hatic double bonds while hydrogenating no more than about 25% of the alkenyl arene aromatic double bonds. Preferred block copolymers are those where at least 99% of the aliphatic double bonds are hydrogenated while less than 5% of the arcmatic double bonds are h~drogenated.
The average molecular weights of the individual blocks may vary within certain lImits. In most instances, ~he monoalkenyl arene blocks will have number average molecular weights between S,OOO and 125,000, pre~erably betw~en 7,000 and 60,000, while the conjugated diene blocks eit~er before or after hydrogenation will have average molecular weiyhts between lO,000 and 300,000, preferably between 30,000 and 150,000. me t~tal average molecular weight of the block copolymr is typically betwaen 25,000 and 250,000, preferably between 35~000 and 200,0000 mese mDlecular weights are most accurately determined by tritium counting methods or osmDtic pressure measurements.
The proportion of the mDnoalXenyl arene blocks should be between about 8 and 55% by weight of the block copolymer, prefer~bly between about lO and 35% by weight.
In addition, the present composition may contain other compc-~ 35 nents such as plasticizers, for example, saturated hydrocarbon or :~
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mineral oils, hydrogenated or saturated hydrocarbon resins along with additives such as stabilizers and oxidation inhibitors.
Aliphatic oils and resins are preferred to aromatic oils and resins since arc~atics tend to cyclicize resulting in colour bcdies.
Preferred oils are primarily aliphatic, saturated mineral oils.
Preferred resins are sa~urated or hydrogenated hydrocarbon resins, such as hydrogenated polymers of dienes and olefins, preferably a styrene-butadiene diblock copolymer. These additional cGmponents must be ccmpa~ible with the block ccpolymer oomponent. The ~election of the other co~ponents depends upon a number of factors, for example, the method for coating a wire.
As stated hereinbefore, the compositions may ke modified with supplement~ry materials such as stabilizers and oxidation inhibitors.
Stabilizers and oxidation inhibitors are ~ypically added to the oompositions in order to protact the polymers against degradation during preparation and use of the composition. Combinations of stabilizers are often m~re effective, due to tha different mechanisms of degradation to which various polymers are subject. Certain sterically hindered phenols, organo-metallic compcunds, aromatic amunes and sulphur compcunds are useful for this purpose. Especially effective types of these materials include the follGwing:-1. Ben2othiazoles, such as 2-(dialkyl-hydroxybenzyl-thio)benzo-thiazoles.
~` 2. Esters of hydroxybenzyl alcohols, such as benzoates, phthalates, stearates, adipates or acrylates of 3,5-diaIkyl~1-hydroxy-kenzyl alcohols.
3. Stannous phenyl catech~lates.
4O Zinc dialkyl dithiocarbamates.
5. Alkylphenols, for exa~ple, 2,6-di-tert-~utyl-4-methylphenol.
~ ~ 30 6. Dilaurylthio-dipropionate (DLTDP~.
; Examples of commercially available antioxidants are "Ionox 220", a trade n~m~ for 4,4-methylene-bis(2,6-di-~-butyl-phenol) and "Ionox 330'1, a trade name for 3,4,6-trisi3,5~di-t-butyl-p-hydroxy-ben2yl)-1,3,5-trimethylbenzene, "Dalpac 4C", a trade name for 2,6-di(t-butyl)-p,cre~ol, "Naugawhite", a trade name for alkylated bisphenol, .~ .
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"Butyl Zimate", a trade name for zinc dibutyl dithiocarbamate, and "Agerite Geltrol", a trad~ name for alkylated-arylated bisphenolic phosphite. From about 0.01 per oent to about S.0 per cent by weight of one or more antioxidants is generally a~ded to the composition.
S Table I hereinafter shows typical, preferred and most preferred contents of oc~ponents (a), (b~, (c) and (d) in the ccmpositions accordiny to the invention, expressed in per cent by weight.
TABLE I
Compone~t Typical Preferred Most Preferred . . ._ . . _ ~al Block Copolymer 5-40 10-30 15-20 (b) Plasticizer ~oil~ 1-20 2-15 4-8 (c~ Mbdified Poly- 1-40 2-20 4-8 propylene (d) Filler 10-85 40-75 63-75 ~e) Functionalized LCW 0.25-10 0.5-5 1-2 ~olecular Weight P~lypropylene ~ax The ~articular amounts of each component may vary somewhat in the resultant oomposition depending on the co~ponents employed and their relative amounts.
` The follcwm g examples further illustrate the invention.
Exam~les 1-11 A The oo~ponents U5ed were as follows:
Block Co~olymer 1 is a S-EB-S~with G2C block molecular weights of ahout 29,000-125,000-29,000.
Rlock Copolymer 2 is a S-EB-S with GæC block molecular weights of about 10,000-50,000-10,000.
Block Copolymer 3 is a S-EB-S with GPC block molecular weights O~ 7,000-35,000-7,000. ~
qhe oil was Penreco 4434 oil available fro~ Penreco Company.
The polypropylene was homopolypropylene PP 5520 from Shell Chemical Ccmpany. The ncdified polypropylene was a maleic anhydride ~ ~ ~raJe ~rk :
.
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13~;~78i 41 functionalized polypropylene, Plexar 2110 frcm Northern Petrochemical Cb~pany in Rolling Meadows, Illinois. ~he ATH was alumuna trihydrate, 1,0 ~m p~ecipitated Hydral 710B frcm Alcoa. The Mg(OH)2 was from Ventron Division of Morton Thiocol Inc. with a secondary (aggregate) S particle ~ize of a~aut 4 ~m. Surface treated Mg(OH)2 was Kisuma 5~
frQm ~yowa Chemical Industry Ltd. which is oleate treated and has a secondary particle (aggregate) size of about 0.8 ~m.
The follcwing antic~idants ~ere used.
Irgano~ lO10; tetra-bismethylene 3-(3,5-ditertbutyl-4 hydroxy-phcnyl)-prGpionate methane from Ciba-Geigy.
Irganox MD-1024; stabilizers from Ciba Geigy.
DLTDP; Plastanox DLTDP, American Cyanamid.
Cc~positions are in per cent by weight.
Exa~ples were extruded Lnsulation coating on 18A~G solid conductor 0.762 mm samples. All insulation coatings were conducbed at 190 C melt temperature.
In E~ample l conventional nonfunctionalized hom~polypropylene was used. Examples 2 to 11 incorporate a maleic anhydride functio-n~lized p~lypropylere. The result~ ere presented ~n Tzble Il.
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dPdP dP dP dP dP dP
N U~ o dP dP dP. dP d~ dP dP
o ~ ~ O
~ ~` I` O O O O 1`
dP dP dP dP dP dP dP
g ~ ~ ~ ) O
I OD O O O O CO ~ ~ ~
dP dP dP dP dP dP dP
~ '-- I 7 ~ I o oO ~ o a~ ~
I~ Ln ~ o o o o ~
~ dP n o d/~ Ch V
O C~l ~ ~ ~ O Ll`) O
~ O O o P P dP P
: ~ ~ ~ ~ O CC~ ~ ~ ~ ~ r~ ) dP dP dP dP dP dP dP
~n o I ~ I ~ oO u~ o n ~ o 1` o o o o cr~
r~
H dP dP dP dP dP dP dP
; ~ ~ '` ~ ¦ ' , U. 8 u~ ,o~ u~ In In ~ ~ ~ ~D .
~ ~ ~ ~ ~ 1` ~ o o o a~ ~ ~ ~ ~ ~ ~
dP dP dP dQ dP dP dP
o~ Oo ~ ~o In cn m 0~ o o o ~ ~1 dP dP dP dP dP dP dP
N U~ 10 0 ,~ ~ ~0 ~ O I
OO~ ~
o o o o In o in ~ o 1~ o ~r o , ,~ ~1 o I o o ~ ~ ~ o ~
co ui I~ O O 0 o ~ D
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me Examples 2 to 11 showed at least a tw~ fold and as high as a three fold increase in the stress at break, compared with Example 1.
The modified polypropylene is much m~re effective m reinforcing these compositions. Each Example contained treated Mg(OH)2 and shcwed good ccmparable physical properties plus good processability.
Co~parative ExEeriments A and B
Ccmparative Experiments A and B were carried GUt as described in Examples 1-11 and Table III. Table III also shows the properties found for oontrol blends ~ith conventional M~(OH)2 and A~H respec-lU tively. These were either not able to be coated or were difficult to process as indicated by the low screw speed and high pcwer input.
:
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:
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TABIE III
Comparative Experiment Block Copolymer Rubber A B
1 14.70% 15.70%
3 __ __ ~: Oil 7.35~ 7.85%
Polypropylene -- --Mbdified Polypropylene 7.35% 7.85%
~ ATX -- 68.00%
: M~(H)2 70.00~ __ ; Surface Treated Mg(OH)2 ~~ ~
IrganGx 1010 0~10% 0.10%
Irganox 1024 0.10% 0.10 DLTDP 0.40~ 0.40%
,~
Stress at Break ~MPa) * 7.79 Elongation at Break (%) * 300 ~e ~ed: (cmis) * --Screw speed (RPM)'J ~ * 20 Pcwer Input (~mpare) * 27 Head Pressure (MPa) * 54.5 Limi~ing Qxygen Index ~ * 30.0 ;* Cbuld not be coated.
' revolutions per minute.
Examples 12-17 were carried out as descr~bed m Examples 1-11 and Table 1~ with the diffexence that a functionaliæed low molecular weight polypropylene wax was used. This wax was functionalized with : 5:: maleic anhydride and was available frcm Eastman Chemical Products ... : ' . ~
.
~ \
~3~7~
Inc. under the trade name "Epolene E43". The results of the exa~ples 12-17 and of Example 1 are stated in Table IV.
Example 1 shows properties of the composition without the functionalized lcw molecular weight polypropylene wax component.
The examples 12 to 17 showed significantly increased tensile strength expressed as stress at break. High~r amounts of the functionalized low molecular wei~ht polypropylene wax tended to produce brittle oampositions.
~ ~ .
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r~ er o o g I g ~I ~ $ r` o ) ~ o o o o o h ,.
1 u> o o o o o s~
~1 1--ir) ~ O g g I g N .--1 N r` O N ~r 2 N
n u1 o o o o o ~
a~ ~r ~r g g $ ~ o N --1 N l~ 0 llt ~ O O O O O N
g 1~ 1 o In r ~ o N ~ N
i ~ Ir~ N O O O 0 1-- N
~ ~ ; ~ ~ o 8 u~ I g In N ~ O ~ ~ ~
~ Lt) U~ N O O O O 1~ ~
g g ' I I ~r u7 ~I-- ~ ~1 o o o o :
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Examples 18-20 Exa~ples 18-20 were carried out as described in Exa~ples 1-11 and Table V with the difference that a functionalized low molecular weight polypropylene wax was used; this wax was the same as that used in Examples 12-17. The results are presented in Table V.
Ccmparison between Example S and Examples 18-20 shows that the presence of said wax allows an increase in stress at break and easier processing as demDnstrated in the decreased head pressure and lower pawer imput in the extruder.
TAELE V
Exa~ple Block CoFolymer Rubber 118.05%17.55%17.05% 16.05%
Oil 4.00% 4-00% 4 % 4 %
~bdified Polypropylene 7.3S% 7.35% 7.35% 7.35%
Functionalized Low MW PP -- 0.50% 1.00% 2.00%
: M~OH)2 Surface treated 70.00% 70.00~70.00% 70.00%
Irganox 1010 0.25% 0.25% 0.25% 0.25%
Irganox 1024 0.10% 0.10% 0.10% 0.10%
DLTDP 0.25% 0.25% 0.25% 0.25%
Stress at Break (MPa) 9.31 9.52 9.58 9.65 : Elongation at Break (%) 330 310 310 220 Lin~ speed ~cm/s) 25 25 25 25 Screw speed (RPM)l)36 30 36 36 PGwer Input ~mpère) 24 23 22.5 23 Head Pressure (MPa)38 34 33 35 ~olutions per minute.
:
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.
AND PROCESS FOR THE PREPAR~TION THEREOF
The invention relates to a flame retardant insulation oomposi-tion and to a pxocess for the p~eparation thereof.
Th~ m~st ocmm~n ~ethod for reducmg the flammability of wire and cable insulation and jacketing materials is the use of an ~;~ S or~anic bromine or chlorine c~mpound alo~g with antimony oxide.
This system is very effective as a flame retard3nt, but such materials produce a dense black smoke when burned, and also produce hydrogen chloride or hydrogen brcmide, which are both corrosi~e and toxic. Because of this, there has been a great deal of lnterest in flame retarded s~stems that produce lower amounts of smoke and to~ic and corrosive gases when they are burned. There appear to be ;~ ~ tw~ main approaches that are beLng followed to met this goal. The first is to elimunate halogens from the system and use instead large loadings of alumina trihydrate, another comm~n fire retardant, or the simQlar filler ~agnesium hydroxide. The second is to de~elop additives that reduce the smoke and acid gas production of the halogenated systems. In addition to low smoke and low toxicity these compositions must also have attractive physical prcperties in order to be used for wire and cable applications. ~hese properties ~ Lnclude hardn~ess, abrasion resistance, environmental stability, deformation rPsistance~ low temperature flexibility, oil resistance and~good e1ectrical properties. At present there are no low-smDke, low-lboxicity, ~lame-retardant materials which are readily available although sQme new materials including metal hydrate filled poly-eth~lene are becoming available.
Mbtal~hydra~ s such as alumina trihydrate and magnesiumtydrc~ide c~ntain water bonded to a crystal s~ructure with the metal atom. When heated to a sufficiently high temperature these cospc~ods decompose and relea~e water which subsequently vaporizes ::, : . :
: .
~ ~ , - ::3L3Vt~ 9, This process of decomposition and vaporization absorbs heat, thus slcwing dcwn the initial heating of the insulation material and consequently slows down the subsequent burning of the material.
After this cooling effect is overwhelmed however, the presence of the metal hydrates has little effect on the subsequent process of burning. Unlike the halogenated flame retardant co~position, metal hydrate compositions with non-halogenated polyolefins break down quickly into monomer units and burn relatively cleanly without a great deal of smoke production. In addition, since metal hydrates only add water to the syst3m, they should not increase the emission of taxic or corrosi~e gases beyona wha~ alread~ would be produced ~y the system.
Magnesium hydroxide fillers along with alumina trihydrate fillers have been used in flame retardant polypropylene co~positions.
Alumina trihydrate is generally more effective as a flame retardant than is magnesium hydroxide due to the greater amount of water incorporated in that filler; however, magnesium hydroxide has specific advantages, for example, better processability when incorporated into a polyolefin co~position and a higher deccmposition temperature than alumina trihydrate (330 C versus 230 C3. This ; increase in deoomposition temperature allows a flame retardant polymer oomposition containing magnesium hydroxide to be processed at a higher temperature than a ccmpound with alumuna trihydrate.
e hi~her processing ten~eratures allow much faster processing due to lower viscosities.
~ Polypropylene, which is readily available at a reasonable ; cost, has found nany industrial uses because of its desirable physical properties, such as easa of fabrication by all conventional methods; high melting pomt of stereoregular, e.g., isotactic, pvlypropylene and compatibility with m~ny other commercial resins, which pernits a large number of blends having specific properties.
Brittleness in these compositions can be reduc~d either by copoly-merizing propylene with ethylene to form block copolymers or by blending hom~polypropylene with rubbers.
`:
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13~)78~
A flame retardant insulation composition has now been found that for~s a self-extinguishing, low smoke and halogen free insulation composition which exhibits high ultimate elongation and is relatively easy to process.
It has been found that functionalizing the polypropylene in an insulation ~lend improves the physical properties, e.g., tensile strength and elongationO It has been found that the brittleness problem can be essen~ially eliminated by using functionalized polypropylene. The functionalized polypropylene has reactive groups grafted to it which will attach to a filler producing bonding between the polypropylene and the filler, thereby producing better physical properties.
; It has also been found that conventional magnesium ~ hydroxide fillers cannot be successfully blended into rubber `; modified polypropylene compositions in the absence of component (e), being a functionalized low molecular weight polypropylene ; wax. These compositions when filled to a reasonable loading of `;; magnesium hydroxide cannot be processed due to agglomeration of the filler particles. When agglomeration occurs the effective ~20 particle size of the filler is increased dramatically and therefore the processability and the properties of the end product are degraded.
Accordingly, it would be desirable to provide a :
; ; magnesium hydroxide filler which has good physical properties and ~ would not adversely affect the processability by agglomeration.
: ,~
.. ~ . . , ` ~3~)78~
Fillers may therefore be surface treated with a coupling agent prior to blending to enhance the bonding between the functionalized polypropylene and the filler.
Furthermore, it has been found that addition of a small amount of a functionalized low molecular weight polypropylene wax to the composition dramatically increases the tensile strength of these compositions.
Accordingly, the present invention provides a flame retardant insulation composition comprising the following components:-(a) in the range of from 5 to 40 percent by weight of a hydrogenated monoalkylarene (A)-conjugated diene (B) block copolymer containing at least two A blocks and at least one B
block;
(b) in the range of from 1 to 20 percent by weight of a saturated hydrocarbon, mineral oil, or a hydrogenated or saturated hydro-carbon resin;
(c) in the range of from 1 to 40 percent by weight of polypropy-lene optionally having an unsaturated polycarboxylic group grafted thereto;
(d) in the range of from 10 to 85 percent by weight of a metal salt hydrate which optionally has been surface treated with a : coupling agent;
(e) and optionally in the range of -from 0.25 to 10 percent by weight of a functionalized low molecular weight polypropylene ~ wax, which composition in the absence of component (e) contains a '~
; ''`"' -, :~
\
~3~7~
- 4a - 63293-272 metal salt hydrate which has been surface treated with a coupling agent.
The compositions of the present invantion are prepared by combining the required components in the correct proportions in conventional blending equip~ent such as a rubber mill or mixer, for example, a Banbury mixer. This is usually done above the melting temperature of the polymeric materials.
The not functionalized polypropylene or homopoly-propylene preferably should be isotactic and may be, for example, of the type corresponding to Shell PP-5944 S*, PP-5520*, and PP
DX-5088*, available from Shell Chemical Company, Houston, Texas.
Most commercial isotactic polypropylenes are suitable in the composition~ of this invention. Syndiotactic homopolymers also can be used.
Functionalized polypropylenes are well known in the art and may be prepared, for examplej according to the procedure described in US patent specification 3,480,580 or 3,481,910.
These polymers may be prepared from homopolypropylene which preferably should be isotactic and may be, for example, the types corresponding to Shell PP-5944 S, PP-5520 and PP DX-5088 mentioned hereinbefore. Syndiotactic homopolymers also can be used. A
preferred functionalized polypropylene is maleic anhydride functionalized polypropylene of the type corresponding to Plexar 2110*, available fro~ Northern Petrochemical Company, Rolling ~ Meadows, Illinois, U.S.A.
; * Trade Mark :
' ~3~7~6~
- 4b - 63293-2722 The fillers used in the present invention are the hydrated inorganic fillers, e.g. hydrated aluminium oxides (A1203.3H20 or Al(OH)3), hydrated magnesia, hydrated calcium silicate zinc borate. Of these compounds, the most preferred are hydrated :
~ i `: :
~ ' ~.3Q78~
alumunium oxide and magnesium hydroxide.
Coupling agent~ may include fatty acid metal salts, for example oleates ox stearates; silanes, maleates, titanates and zirco-aluminates.
The filler particle size is relatively non-important and may be in accordance with those sizes used by the prior art. Preferred particle sizes axe less than 5 ~m. It has also been found that magnesium hydroxide fillers with a high aspect ratio crystallate shape and larger size are also less likely to agglomerate than those with a lower aspect ratio. Aspect ratios ~or the crystallites should be greater than 4 and mean secondary particle (agglcmerateJ
size should be less than 3 ~m and are preferably in the range of from 0.6 to 1.2 ~m.
Functionalized low molecular weight polypropylene waxes are well kncwn in the art and may be prepared, for example, from polymers prepared according to the procedures described in UOS.
pat~nt specifications 2,969,345 and 3,919,176. me ccnpositions according to the invention and containing such waxes preferably cGntain not functionalized polypropylene and may contain not functionalized polypropylene as well as functionalized polypxolylene.
A particularly preferred functionalized low molecular weight polypropylene wax is a normally solid thermoplastic ethylene-based polymer modified by monomers having reactive carboxylic acid groups, particularly a copol~mer of a ma~or proportion of ethylene and a m mor proportion, typically from 1 to 30, preferably from 2 to 20~ per cent by weight, of an ethylenically unsaturated carboxylic acid. Specific examples of such suit~ble ethylenically unsaturated carboKylic acids (which term includes mono- and polybasic acids, ~; ~ 30 acid anhydrides, and partial esters of polybasic aci~s) are acrylic a¢id, methacrylic acid, crDtonic acid, fumaric acid, maleic acid, itaoonic acid, maleic anhydride monomethyl maleate, monoethyl maleate, manomethyl fumarate, n~noethyl fumarat~e, tripropylene glycol monome~hyl ether acid maleate, or ethylene glycol moncphenyl ether acid maleate. The carbcxylic acid ~Dnomer is preferably selected from ~,B-ethylem cally unsaturated mono- and polycarboxylic acids and acid anhydrides having from 3 to 8 carbon atoms per .
~3~7~
molecule and partial esters of such polycarboxylic acids wherein the acid moiety has at least one carboxylic acid ~roup and the alcohol moiety has from 1 to 20 carbon atoms. me copolymer can also contain other copolymerizable monomers including an ester of acrylic acid. The comonomers can be co~bined in the copolymer in any way, for example, as random copolymers, as block or sequential copolymers, or as ~raft copolymers. Materials of these kinds and methods of making them are readily known in the art. Specific exa~ples of such copolymers are ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer, ethylene maleic acid copolymer and the like~
Functionalized low molecular weight polyprcpylene wax is available from, for example, Eastman Chemical Products Inc. under the trade name "Epolene E43"~
The hydrogenated monoalkyl arene-conjugated diene block copolymers useful in the present invention are well known in the art. m is block copolymer, for example, as defined in U.S. patent specification 4,110,303, has at least two monoalkenyl arene polymer end blocks A and at least one polymer mid block B of a substantially campletely hydrogenated conjugated diene polymer block, an ethylene-propylene polymer block or an ethylene-butene polymer block. me block copolymers employed in the present invention may have a variet~ of geometrical structures, since the invention doe s not depend on any specific geometrical struct.ure, but rather upon the chemical constitution of each of the polymer blocks. mus, the structures may be lmear, radial or branched so long as each copolymer has at least two polymer end blocks A and at least one polymEr mdd block B as defined hereinbefore. Methods for the preparation of such polymers are known in the art. Particular ~ 30 reference will be made to the use of lithium based catalysts and; ~ especially lithium alkyls for the preparation of the precursor polymers ~polymers before hydrogenation). U.S. patent specification 3,595,942 not only describes some of the polymers of the present invention but also describes suitable methods for their hydro-genation. rrhe structure of the polymers is determined by their method of polymerization. For example, linear polymers result by : .
:
13~8~9~
sequ~ntial introduction of the desired monomers into the reaction vessel when using such initiators as lithium-aLkyls or dilithio-stilbene and the like, or by coupling a two segment block copolymer with a difuntional coupling agent. Branched structures, on the other hand, may be obtained by the use of suitable coupling agents having a func*ionalit~v with respect to the precursor polymers of three or more. Cbupling may be effected with multifunctional coupling agents such as dihaloalkanes or alkenes and divinylbenzene as well as certain polar compDunds such as silicon halides, siloxanes or esters of monohydric alcohols with carbcxylic acids. The presence of any coupling residues in the polymer may be ignored for an ad~quate description of the polymers forming a part of the ccmpo-sitions of this invention. Likewise, in the generic sense, the specific structures also may be ignored. The invention applies especially to the use of selectively hydrogenated polymers having the configuration before hydrogenation of the following typical species:
polystyrene-polybutadiene-polystyrene (SBS) polystyrene-polyisoprene-polystyrene (SIS) poly(alpha-methylstyrene)-polybutadiene~poly(alpha-methylstyrene) and poly(alpha-methylstyrene)-polyisoprene-poly(alpha-methylstyrene).
It will be understood that both blocks A and B may be either homcpolymer or random cqpoly~er blocks as long as each block predomunat~s in at least one class of the monomers characterizing ~he blocks and as long as the A blocks individually predcminate in m~noalkenyl anenes and the B blocks individually predom~nate in dienes. me term "~noaIkenyl arene" ~ill be taken to include ; ~ especially styrene and its analogs and hom~lc~s including alpha-methylstyrene and ring-substituted styrenes, particularly ring-methylated styrenes. The preferred m~noalkenyl arenes are styrene and alpha-methylstyrene, and styrene is particularly preferred. me blocks B may oompris~ homopolymers of butadiene or isoprene and capolymers of one of these tw~ dienes with a monoalkenyl arene as ~; 35 long as the blocks B predcminate in conjugated diene units. When the monomer enployed is butadiene, it is preferred that between ~:
~.
:
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about 35 and about 55 mol per cent of the condensed butadiene units in the butadiene polymer block have l,2 configuration. Thus, when such a block is hydrogenated, the resulting product is, or resembles a regular copolymer block of ethylene and l-butene (EB). If the conjugated diene employed is isoprene, the resulting hydrogenated product is or resembles a regular copolymer block of ethylene and propylene (EP). Ethylene-butene or ethylene-propylene blocks prepared via direct polymerization and not by hydrogenation of conjugated diene polymer blocks are also contemplated by the present invention.
Hydrogenation of the precursor block copolymers, if required, is preferably effected by use of a catalyst comprising the reaction pro~ucts of an aluminium alkyl compound with nickel or cobalt carboxylates or alko~ides under such conditions as-to substantially completely hydrogenate at least 80% of the ali~hatic double bonds while hydrogenating no more than about 25% of the alkenyl arene aromatic double bonds. Preferred block copolymers are those where at least 99% of the aliphatic double bonds are hydrogenated while less than 5% of the arcmatic double bonds are h~drogenated.
The average molecular weights of the individual blocks may vary within certain lImits. In most instances, ~he monoalkenyl arene blocks will have number average molecular weights between S,OOO and 125,000, pre~erably betw~en 7,000 and 60,000, while the conjugated diene blocks eit~er before or after hydrogenation will have average molecular weiyhts between lO,000 and 300,000, preferably between 30,000 and 150,000. me t~tal average molecular weight of the block copolymr is typically betwaen 25,000 and 250,000, preferably between 35~000 and 200,0000 mese mDlecular weights are most accurately determined by tritium counting methods or osmDtic pressure measurements.
The proportion of the mDnoalXenyl arene blocks should be between about 8 and 55% by weight of the block copolymer, prefer~bly between about lO and 35% by weight.
In addition, the present composition may contain other compc-~ 35 nents such as plasticizers, for example, saturated hydrocarbon or :~
. , 78~i~
mineral oils, hydrogenated or saturated hydrocarbon resins along with additives such as stabilizers and oxidation inhibitors.
Aliphatic oils and resins are preferred to aromatic oils and resins since arc~atics tend to cyclicize resulting in colour bcdies.
Preferred oils are primarily aliphatic, saturated mineral oils.
Preferred resins are sa~urated or hydrogenated hydrocarbon resins, such as hydrogenated polymers of dienes and olefins, preferably a styrene-butadiene diblock copolymer. These additional cGmponents must be ccmpa~ible with the block ccpolymer oomponent. The ~election of the other co~ponents depends upon a number of factors, for example, the method for coating a wire.
As stated hereinbefore, the compositions may ke modified with supplement~ry materials such as stabilizers and oxidation inhibitors.
Stabilizers and oxidation inhibitors are ~ypically added to the oompositions in order to protact the polymers against degradation during preparation and use of the composition. Combinations of stabilizers are often m~re effective, due to tha different mechanisms of degradation to which various polymers are subject. Certain sterically hindered phenols, organo-metallic compcunds, aromatic amunes and sulphur compcunds are useful for this purpose. Especially effective types of these materials include the follGwing:-1. Ben2othiazoles, such as 2-(dialkyl-hydroxybenzyl-thio)benzo-thiazoles.
~` 2. Esters of hydroxybenzyl alcohols, such as benzoates, phthalates, stearates, adipates or acrylates of 3,5-diaIkyl~1-hydroxy-kenzyl alcohols.
3. Stannous phenyl catech~lates.
4O Zinc dialkyl dithiocarbamates.
5. Alkylphenols, for exa~ple, 2,6-di-tert-~utyl-4-methylphenol.
~ ~ 30 6. Dilaurylthio-dipropionate (DLTDP~.
; Examples of commercially available antioxidants are "Ionox 220", a trade n~m~ for 4,4-methylene-bis(2,6-di-~-butyl-phenol) and "Ionox 330'1, a trade name for 3,4,6-trisi3,5~di-t-butyl-p-hydroxy-ben2yl)-1,3,5-trimethylbenzene, "Dalpac 4C", a trade name for 2,6-di(t-butyl)-p,cre~ol, "Naugawhite", a trade name for alkylated bisphenol, .~ .
.~,: ~,. ...
~3~8~;~
"Butyl Zimate", a trade name for zinc dibutyl dithiocarbamate, and "Agerite Geltrol", a trad~ name for alkylated-arylated bisphenolic phosphite. From about 0.01 per oent to about S.0 per cent by weight of one or more antioxidants is generally a~ded to the composition.
S Table I hereinafter shows typical, preferred and most preferred contents of oc~ponents (a), (b~, (c) and (d) in the ccmpositions accordiny to the invention, expressed in per cent by weight.
TABLE I
Compone~t Typical Preferred Most Preferred . . ._ . . _ ~al Block Copolymer 5-40 10-30 15-20 (b) Plasticizer ~oil~ 1-20 2-15 4-8 (c~ Mbdified Poly- 1-40 2-20 4-8 propylene (d) Filler 10-85 40-75 63-75 ~e) Functionalized LCW 0.25-10 0.5-5 1-2 ~olecular Weight P~lypropylene ~ax The ~articular amounts of each component may vary somewhat in the resultant oomposition depending on the co~ponents employed and their relative amounts.
` The follcwm g examples further illustrate the invention.
Exam~les 1-11 A The oo~ponents U5ed were as follows:
Block Co~olymer 1 is a S-EB-S~with G2C block molecular weights of ahout 29,000-125,000-29,000.
Rlock Copolymer 2 is a S-EB-S with GæC block molecular weights of about 10,000-50,000-10,000.
Block Copolymer 3 is a S-EB-S with GPC block molecular weights O~ 7,000-35,000-7,000. ~
qhe oil was Penreco 4434 oil available fro~ Penreco Company.
The polypropylene was homopolypropylene PP 5520 from Shell Chemical Ccmpany. The ncdified polypropylene was a maleic anhydride ~ ~ ~raJe ~rk :
.
.~
13~;~78i 41 functionalized polypropylene, Plexar 2110 frcm Northern Petrochemical Cb~pany in Rolling Meadows, Illinois. ~he ATH was alumuna trihydrate, 1,0 ~m p~ecipitated Hydral 710B frcm Alcoa. The Mg(OH)2 was from Ventron Division of Morton Thiocol Inc. with a secondary (aggregate) S particle ~ize of a~aut 4 ~m. Surface treated Mg(OH)2 was Kisuma 5~
frQm ~yowa Chemical Industry Ltd. which is oleate treated and has a secondary particle (aggregate) size of about 0.8 ~m.
The follcwing antic~idants ~ere used.
Irgano~ lO10; tetra-bismethylene 3-(3,5-ditertbutyl-4 hydroxy-phcnyl)-prGpionate methane from Ciba-Geigy.
Irganox MD-1024; stabilizers from Ciba Geigy.
DLTDP; Plastanox DLTDP, American Cyanamid.
Cc~positions are in per cent by weight.
Exa~ples were extruded Lnsulation coating on 18A~G solid conductor 0.762 mm samples. All insulation coatings were conducbed at 190 C melt temperature.
In E~ample l conventional nonfunctionalized hom~polypropylene was used. Examples 2 to 11 incorporate a maleic anhydride functio-n~lized p~lypropylere. The result~ ere presented ~n Tzble Il.
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dPdP dP dP dP dP dP
N U~ o dP dP dP. dP d~ dP dP
o ~ ~ O
~ ~` I` O O O O 1`
dP dP dP dP dP dP dP
g ~ ~ ~ ) O
I OD O O O O CO ~ ~ ~
dP dP dP dP dP dP dP
~ '-- I 7 ~ I o oO ~ o a~ ~
I~ Ln ~ o o o o ~
~ dP n o d/~ Ch V
O C~l ~ ~ ~ O Ll`) O
~ O O o P P dP P
: ~ ~ ~ ~ O CC~ ~ ~ ~ ~ r~ ) dP dP dP dP dP dP dP
~n o I ~ I ~ oO u~ o n ~ o 1` o o o o cr~
r~
H dP dP dP dP dP dP dP
; ~ ~ '` ~ ¦ ' , U. 8 u~ ,o~ u~ In In ~ ~ ~ ~D .
~ ~ ~ ~ ~ 1` ~ o o o a~ ~ ~ ~ ~ ~ ~
dP dP dP dQ dP dP dP
o~ Oo ~ ~o In cn m 0~ o o o ~ ~1 dP dP dP dP dP dP dP
N U~ 10 0 ,~ ~ ~0 ~ O I
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o o o o In o in ~ o 1~ o ~r o , ,~ ~1 o I o o ~ ~ ~ o ~
co ui I~ O O 0 o ~ D
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me Examples 2 to 11 showed at least a tw~ fold and as high as a three fold increase in the stress at break, compared with Example 1.
The modified polypropylene is much m~re effective m reinforcing these compositions. Each Example contained treated Mg(OH)2 and shcwed good ccmparable physical properties plus good processability.
Co~parative ExEeriments A and B
Ccmparative Experiments A and B were carried GUt as described in Examples 1-11 and Table III. Table III also shows the properties found for oontrol blends ~ith conventional M~(OH)2 and A~H respec-lU tively. These were either not able to be coated or were difficult to process as indicated by the low screw speed and high pcwer input.
:
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:
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TABIE III
Comparative Experiment Block Copolymer Rubber A B
1 14.70% 15.70%
3 __ __ ~: Oil 7.35~ 7.85%
Polypropylene -- --Mbdified Polypropylene 7.35% 7.85%
~ ATX -- 68.00%
: M~(H)2 70.00~ __ ; Surface Treated Mg(OH)2 ~~ ~
IrganGx 1010 0~10% 0.10%
Irganox 1024 0.10% 0.10 DLTDP 0.40~ 0.40%
,~
Stress at Break ~MPa) * 7.79 Elongation at Break (%) * 300 ~e ~ed: (cmis) * --Screw speed (RPM)'J ~ * 20 Pcwer Input (~mpare) * 27 Head Pressure (MPa) * 54.5 Limi~ing Qxygen Index ~ * 30.0 ;* Cbuld not be coated.
' revolutions per minute.
Examples 12-17 were carried out as descr~bed m Examples 1-11 and Table 1~ with the diffexence that a functionaliæed low molecular weight polypropylene wax was used. This wax was functionalized with : 5:: maleic anhydride and was available frcm Eastman Chemical Products ... : ' . ~
.
~ \
~3~7~
Inc. under the trade name "Epolene E43". The results of the exa~ples 12-17 and of Example 1 are stated in Table IV.
Example 1 shows properties of the composition without the functionalized lcw molecular weight polypropylene wax component.
The examples 12 to 17 showed significantly increased tensile strength expressed as stress at break. High~r amounts of the functionalized low molecular wei~ht polypropylene wax tended to produce brittle oampositions.
~ ~ .
' ~3~7~
r~ er o o g I g ~I ~ $ r` o ) ~ o o o o o h ,.
1 u> o o o o o s~
~1 1--ir) ~ O g g I g N .--1 N r` O N ~r 2 N
n u1 o o o o o ~
a~ ~r ~r g g $ ~ o N --1 N l~ 0 llt ~ O O O O O N
g 1~ 1 o In r ~ o N ~ N
i ~ Ir~ N O O O 0 1-- N
~ ~ ; ~ ~ o 8 u~ I g In N ~ O ~ ~ ~
~ Lt) U~ N O O O O 1~ ~
g g ' I I ~r u7 ~I-- ~ ~1 o o o o :
M 3 ~
~, , ~, ~
, ~ .
~: :
- . . .
- . . . .
.
~ . .
. - . . ... .
.
.
~3~'~8~
Examples 18-20 Exa~ples 18-20 were carried out as described in Exa~ples 1-11 and Table V with the difference that a functionalized low molecular weight polypropylene wax was used; this wax was the same as that used in Examples 12-17. The results are presented in Table V.
Ccmparison between Example S and Examples 18-20 shows that the presence of said wax allows an increase in stress at break and easier processing as demDnstrated in the decreased head pressure and lower pawer imput in the extruder.
TAELE V
Exa~ple Block CoFolymer Rubber 118.05%17.55%17.05% 16.05%
Oil 4.00% 4-00% 4 % 4 %
~bdified Polypropylene 7.3S% 7.35% 7.35% 7.35%
Functionalized Low MW PP -- 0.50% 1.00% 2.00%
: M~OH)2 Surface treated 70.00% 70.00~70.00% 70.00%
Irganox 1010 0.25% 0.25% 0.25% 0.25%
Irganox 1024 0.10% 0.10% 0.10% 0.10%
DLTDP 0.25% 0.25% 0.25% 0.25%
Stress at Break (MPa) 9.31 9.52 9.58 9.65 : Elongation at Break (%) 330 310 310 220 Lin~ speed ~cm/s) 25 25 25 25 Screw speed (RPM)l)36 30 36 36 PGwer Input ~mpère) 24 23 22.5 23 Head Pressure (MPa)38 34 33 35 ~olutions per minute.
:
~.:
: :
~ ~ , ~ ` ' ' , ' .
.
Claims (14)
1. A flame retardant insulation composition comprising the following components:-(a) in the range of from 5 to 40 percent by weight of a hydrogenated monoalkylarene (A)-conjugated diene (B) block copolymer containing at least two A blocks and at least one B
block;
(b) in the range of from 1 to 20 percent by weight of a saturated hydrocarbon, mineral oil, or a hydrogenated or saturated hydrocarbon resin;
(c) in the range of from 1 to 40 percent by weight of polypropylene optionally having an unsaturated polycarboxylic group grafted thereto;
(d) in the range of from 10 to 85 percent by weight of a metal salt hydrate which optionally has been surface treated with a coupling agent;
(e) and optionally in the range of from 0.25 to 10 percent by weight of a functionalized low molecular weight polypropylene wax, which composition in the absence of component (e) contains a metal salt hydrate which has been surface treated with a coupling agent.
- 18a - 63293-2722
block;
(b) in the range of from 1 to 20 percent by weight of a saturated hydrocarbon, mineral oil, or a hydrogenated or saturated hydrocarbon resin;
(c) in the range of from 1 to 40 percent by weight of polypropylene optionally having an unsaturated polycarboxylic group grafted thereto;
(d) in the range of from 10 to 85 percent by weight of a metal salt hydrate which optionally has been surface treated with a coupling agent;
(e) and optionally in the range of from 0.25 to 10 percent by weight of a functionalized low molecular weight polypropylene wax, which composition in the absence of component (e) contains a metal salt hydrate which has been surface treated with a coupling agent.
- 18a - 63293-2722
2. A composition as claimed in claim 1 wherein the block copolymer is a hydrogenated styrene-butadiene-styrene block copolymer.
3. A composition as claimed in claim 1 or 2 wherein the polypropylene is maleic anhydride functionalized.
4. A composition as claimed in claim 1 or 2 wherein the plasticizer is a mineral oil or a styrene butadiene diblock copolymer.
5. A composition as claimed in claim 1 or 2 wherein the filler is alumina trihydrate.
6. A composition as claimed in claim 1 or 2 wherein the filler is magnesium hydroxide.
7. A composition as claimed in claim 1 wherein the coupling agent is a fatty acid metal salt, a maleate, a silane, a titanate or a zirco-aluminate.
8. A composition as claimed in claim 7 wherein the coupling agent is an oleate or a stearate.
9. A composition as claimed in claim 1 or 2 wherein the hydrated magnesium hydroxide has a mean secondary particle size in the range of from 0.6 to 1.2 µm.
10. A composition as claimed in claim 1 or 2 wherein the hydrated magnesium hydroxide has a crystallite aspect ratio greater than 4.
11. A composition as claimed in claim 1 or 2 wherein the functionalized low molecular weight polypropylene wax is a maleic anhydride functionalized low molecular weight polypropylene wax.
12. A composition as claimed in claim 1 which comprises in the range of from 15 to 20 weight percent of component (a), 4 to 8 weight percent of component (b), 4 to 8 weight percent of component (c) and 63 to 75 weight percent of component (d).
13. A composition as claimed in claim 12 which also comprises in the range of from 0.5 to 5 weight percent of component (e).
14. A process for the preparation of a flame retardant insulation composition as claimed in claim 1 or 2 which process comprises combining (a) in the range of from 5 to 40 percent by weight of a hydrogenated monoalkylarene (A)-conjugated diene (B) block copolymer containing at least two A blocks and at least one block;
(b) in the range of from 1 to 20 percent by weight of a saturated hydrocarbon, mineral oil, or a hydrogenated or saturated hydrocarbon resin;
(c) in the range of from 1 to 40 percent by weight of polypropylene optionally having an unsaturated polycarboxylic group grafted thereto;
(d) in the range of from 10 to 85 percent by weight of a metal salt hydrate which optionally has been surface treated with a coupling agent;
(e) and optionally in the range of from 0.25 to 10 percent by weight of a functionalized low molecular weight polypropylene wax, which composition in the absence of component (e) contains a metal salt hydrate which has been surface treated with a coupling agent.
(b) in the range of from 1 to 20 percent by weight of a saturated hydrocarbon, mineral oil, or a hydrogenated or saturated hydrocarbon resin;
(c) in the range of from 1 to 40 percent by weight of polypropylene optionally having an unsaturated polycarboxylic group grafted thereto;
(d) in the range of from 10 to 85 percent by weight of a metal salt hydrate which optionally has been surface treated with a coupling agent;
(e) and optionally in the range of from 0.25 to 10 percent by weight of a functionalized low molecular weight polypropylene wax, which composition in the absence of component (e) contains a metal salt hydrate which has been surface treated with a coupling agent.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80280685A | 1985-11-27 | 1985-11-27 | |
| US80279785A | 1985-11-27 | 1985-11-27 | |
| US802,806 | 1985-11-27 | ||
| US802,797 | 1985-11-27 | ||
| US814,705 | 1985-12-30 | ||
| US06/814,705 US4622352A (en) | 1985-12-30 | 1985-12-30 | Low smoke modified polypropylene insulation compositions |
| US814,706 | 1985-12-30 | ||
| US06/814,706 US4622350A (en) | 1985-12-30 | 1985-12-30 | Low smoke polypropylene insulation compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1307864C true CA1307864C (en) | 1992-09-22 |
Family
ID=27505819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000522194A Expired - Fee Related CA1307864C (en) | 1985-11-27 | 1986-11-05 | Low smoke modified polypropylene insulation compositions and process for the preparation thereof |
Country Status (11)
| Country | Link |
|---|---|
| EP (2) | EP0427352A1 (en) |
| JP (1) | JPH0798888B2 (en) |
| AU (1) | AU585096B2 (en) |
| BR (1) | BR8605782A (en) |
| CA (1) | CA1307864C (en) |
| DE (1) | DE3688454T2 (en) |
| DK (1) | DK565386A (en) |
| ES (1) | ES2054615T3 (en) |
| FI (1) | FI89603C (en) |
| NO (1) | NO172055C (en) |
| NZ (1) | NZ218397A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4783504A (en) * | 1986-02-28 | 1988-11-08 | Shell Oil Company | Hot melt adhesive containing a silane grafted hydrogenated block polymer |
| JPH0778155B2 (en) * | 1987-12-24 | 1995-08-23 | 住友化学工業株式会社 | Thermoplastic elastomer composition |
| US5260366A (en) * | 1987-12-24 | 1993-11-09 | Sumitomo Chemical Company, Limited | Thermoplastic elastomer composition and process for producing same |
| TW222014B (en) * | 1992-02-13 | 1994-04-01 | Shell Internat Res Schappej B V | |
| US5288785A (en) * | 1993-06-14 | 1994-02-22 | Union Carbide Chemicals & Plastics Technology Corporation | Low voltage power cables |
| US5561185A (en) * | 1993-11-12 | 1996-10-01 | The Furukawa Electric Co., Ltd. | Fire-retardant resin composition and a covered electric wire |
| GB9504705D0 (en) * | 1995-03-08 | 1995-04-26 | Scapa Group Plc | Wire coating composition |
| AU733739B2 (en) * | 1997-10-01 | 2001-05-24 | Kyowa Chemical Industry Co., Ltd. | Flame retardant resin composition |
| US6576160B1 (en) | 1998-09-14 | 2003-06-10 | Hans-Jurgen Eichler | Surface-modified filling material composition |
| JP2001200106A (en) * | 1999-03-02 | 2001-07-24 | Jsr Corp | Flame-retarded polymer composition |
| JP4503811B2 (en) * | 2000-11-10 | 2010-07-14 | 株式会社ブリヂストン | Heat dissipation elastomer composition and heat dissipation sheet |
| US6646205B2 (en) | 2000-12-12 | 2003-11-11 | Sumitomo Wiring Systems, Ltd. | Electrical wire having a resin composition covering |
| WO2016031550A1 (en) * | 2014-08-26 | 2016-03-03 | 株式会社クラレ | Thermoplastic polymer composition, and moudled article |
| WO2022138522A1 (en) * | 2020-12-25 | 2022-06-30 | Ｅｎｅｏｓ株式会社 | Thermoplastic elastomer composition and molded body |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3271340A (en) * | 1960-12-30 | 1966-09-06 | Eastman Kodak Co | Olefin polymers modified with polypropylene wax |
| US3480580A (en) * | 1965-10-22 | 1969-11-25 | Eastman Kodak Co | Modified polymers |
| US3464850A (en) * | 1966-04-25 | 1969-09-02 | Shell Oil Co | Fibrous organic material bonded with a block copolymer |
| US3793283A (en) * | 1972-03-16 | 1974-02-19 | Shell Oil Co | Impact-improved polypropylene compositions |
| US3830767A (en) * | 1973-05-02 | 1974-08-20 | Shell Oil Co | Block copolymer compositions |
| US4006116A (en) * | 1975-11-26 | 1977-02-01 | Shell Oil Company | Block copolymer compositions and articles |
| US4373039A (en) * | 1980-06-11 | 1983-02-08 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Elastomer coated fillers and composites thereof comprising at least 60% by wt. of a hydrated filler and an elastomer containing an acid substituent |
| JPS5911332A (en) * | 1982-07-12 | 1984-01-20 | Showa Denko Kk | Blending of thermoplastic resin with additive |
| JPS60133039A (en) * | 1983-12-21 | 1985-07-16 | Mitsubishi Petrochem Co Ltd | Thermoplastic resin composition |
| JPS60170651A (en) * | 1984-02-16 | 1985-09-04 | Hitachi Cable Ltd | Non-corrosive flame-retardant resin composition |
-
1986
- 1986-11-05 CA CA000522194A patent/CA1307864C/en not_active Expired - Fee Related
- 1986-11-19 EP EP90203003A patent/EP0427352A1/en not_active Withdrawn
- 1986-11-19 DE DE19863688454 patent/DE3688454T2/en not_active Expired - Fee Related
- 1986-11-19 EP EP86202048A patent/EP0227139B1/en not_active Expired - Lifetime
- 1986-11-19 ES ES86202048T patent/ES2054615T3/en not_active Expired - Lifetime
- 1986-11-25 FI FI864793A patent/FI89603C/en not_active IP Right Cessation
- 1986-11-25 DK DK565386A patent/DK565386A/en not_active Application Discontinuation
- 1986-11-25 NZ NZ21839786A patent/NZ218397A/en unknown
- 1986-11-25 NO NO864720A patent/NO172055C/en unknown
- 1986-11-25 BR BR8605782A patent/BR8605782A/en not_active IP Right Cessation
- 1986-11-25 AU AU65667/86A patent/AU585096B2/en not_active Ceased
- 1986-11-25 JP JP61280530A patent/JPH0798888B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798888B2 (en) | 1995-10-25 |
| DE3688454D1 (en) | 1993-06-24 |
| AU6566786A (en) | 1987-06-04 |
| ES2054615T3 (en) | 1994-08-16 |
| AU585096B2 (en) | 1989-06-08 |
| FI89603B (en) | 1993-07-15 |
| JPS62131052A (en) | 1987-06-13 |
| FI864793A (en) | 1987-05-28 |
| DK565386D0 (en) | 1986-11-25 |
| NO172055B (en) | 1993-02-22 |
| EP0227139A2 (en) | 1987-07-01 |
| EP0427352A1 (en) | 1991-05-15 |
| NZ218397A (en) | 1989-06-28 |
| EP0227139A3 (en) | 1988-11-09 |
| NO172055C (en) | 1993-06-02 |
| FI864793A0 (en) | 1986-11-25 |
| BR8605782A (en) | 1987-08-25 |
| DE3688454T2 (en) | 1993-09-30 |
| EP0227139B1 (en) | 1993-05-19 |
| DK565386A (en) | 1987-05-28 |
| NO864720D0 (en) | 1986-11-25 |
| FI89603C (en) | 1993-10-25 |
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